Nonexchangeable potassium extraction and associated structural changes of mica dominant clay minerals

Abstract

Six mica dominant soils representing a landform sequence were used for the present investigation. The effect of extraction of nonexchangeable potassium (K) by boiling 1 M HNO₃ treatment and its associated structural changes of micaceous clay minerals was studied by employing x‐ray diffraction technique. Potassium release was rapid in the first three extractions and slowed down to a constant rate thereafter in all the clay samples. The first extraction contributed about 45.57–62.69% towards the total K release. The calculated values of rate constant (first order) decreased sharply from 0.065–0.025 min^‐1 after third extraction and reached a constant value thereafter. The calculated integral width of first order reflection of mica peak (10Å) decreased considerably with nitric acid treatment, but no such effect was observed in 5Å peak. The differential x‐ray diffraction (DXRD) traces showed that the HNO₃ treatment dissolved finer particles of mica particularly trioctahedral component and mixed layer minerals, smectite, chlorite and vermiculite.     

The geochemistry of black water in selected coastal streams of the Southeastern United States

Abstract

An investigation was conducted in a watershed formed by the tributaries of the Little River in South Georgia to study the nature of the humic and inorganic fractions of black water, and their influence on stream water quality. Large amounts of black colored water were sampled during 1983 to 1984 according to streamflow pattern in December, March, June and September. Measurements of air and water temperature and dissolved oxygen were made at the gaging sites, whereas water analysis for conductivity, Cl, NO₃‐N, NH₄‐N, P, total N, and other macro‐ and microelements were conducted in the laboratory. Fulvic (FA) and humic acid (HA) were isolated from the water samples, and analyzed by infrared and ¹³C NMR spectroscopy. Suspended clay from the water samples were collected and determined by x‐ray diffraction analysis. The results showed that black water was characterized by low conductivity and low ion concentrations indicating satisfactory chemical quality. The Na content was half the amount of other rivers in the Southeastern United States, whereas the ? content was similar to the world average. A seasonal fluctuation was noticed for Ca and Mg concentration. The increase of these ions during high streamflow in spring and summer was attributed to agricultural practices in the surrounding lands. Dissolved organic matter (DOM) concentration was highest in December during low streamflow. As DOM content decreased during high streamflow, water pH increased. A large part of the humified DOM was composed of fulvic acid, which was more aromatic in nature than soil‐fulvic acid as determined by ¹³C NMR. The suspended clay had a composition reflecting the clay mineralogy of Tifton soils in the surrounding uplands. It is believed that the Tifton soil, with its low activity clay and hence low CEC, may not be able to buffer the effect of acid leaching of black water.     

Clay mineralogical and ammonium fixation characteristics of some tropical upland rice soils

Abstract

In view of the agronomic and economic significance of NH₄ fixation in soils, an attempt has been made to relate this to the most reactive mineral constituents of soils ‐ the clay minerals, under the temperature‐moisture regimes normal to tropical upland rice soils. Laboratory fixation study was done with NH₄, concentrations similar to those common in soils upon N fertilization, and under alternate wetting and drying at ambient temperatures rather than at 100°C as in many published studies.

Results of the investigation show that soil clays with dominant vermiculite and montmorillonite fix the greatest proportion of applied NH₄ (94 and 91%), followed by beidellite (72%) and x‐ray amorphous (45–64%) clays. Fixation is negligible (10%) in the clay with mineral suite consisting of hydrous mica, halloysite, and chlorite. Crystallinity of minerals seems to influence NH₄ fixation appreciably.     

Disintegration of the clay fraction in the eluvial horizons of some Danish podzolized soils

Abstract

Using sequential extractions, total elemental analysis, and X‐ray diffraction, we have investigated the impact of the podzolization process on component composition of the clay fraction in the eluvial horizons of eight more or less podzolized Danish soils. The results indicate that podzolization is highly aggressive towards all clay components in the eluvial horizons eventually leading to their disintegration. The 2:1 layer silicate clay minerals, illite and chlorite, are first transformed into other 2:1 layer silicate clay minerals. After passing through a microcrystalline phase high in Si but low in Al, Fe, Mg, and K, they finally disintegrate completely. Even gibbsite and kaolinite disintegrate under the aggressive conditions, caused among other things by the presence of dissolved complex forming organic molecules in these horizons. Application of lime and fertilizers seems to be able to reverse the process in case of the 2:1 layer silicate clay minerals.     

Zinc adsorption characteristics of selected calcareous soils of Iran and their relationship with soil properties

Abstract

The apparent recovery of applied zinc (Zn) by plants is very low in calcareous soils of Iran because most of it is retained by the soil solids. Subsamples of 24 surface soil (clay 130–530 g kg^‐1; pH 7.7–8.4; electrical conductivity 0.63–3.10 dS m^‐1; organic matter 6.0–22.0 g kg^‐1; cation exchange capacity 8–20 cmol kg^‐1; calcium carbonate (CaCO₃) equivalent 180–460 g kg^‐1) representing 13 soil series in three taxonomic orders were equilibrated with zinc sulphate (ZnSO₄) solutions and the amount of Zn disappeared from solution after a 24‐h shaking period was taken as that adsorbed (retained) by the soil solids. The adsorption data were fitted to Freundlich (X=AC^B) and Langmuir [X=(K‐bC)/(1+K#lbC)] adsorption isotherms. Backward stepwiseprocedure was used to obtain regression equations with isotherms coefficients as dependent and soil properties as independent variables. Freundlich A and Langmuir K were found to be highly significantly related to pH and clay and increasing as these soil properties increased. But Langmuir b was related only to clay and Freundlich B showed no significant relationship with any of the properties studied. The distribution coefficient (also called maximum buffering capacity), calculated as the product of Langmuir K and b, was also found to be highly significantly related to pH and clay. It is concluded that pH and clay content of calcareous soils are the most influential soil properties in retention of Zn.     

A comparison between X‐ray fluorescence and dissolution methods employing lithium metaborate fusion for elemental analysis of soil clays

Abstract

A method employing fusion of soil clay samples with lithium metaborate (1:5 ratio) in a furnace at 1050°C for 1 hr. subsequent dissolution of the fused sample in 4% HNO₃. and elemental analysis for Si, Al, Fe, Ca, Mg, K, and Ti by atomic absorption spectrometry was compared with the X‐ray fluorescence (XRF) fused disc technique for analysis. Duplicated analyses were performed on 15 clay samples from soils of the southern U.S and three API reference samples. The mean total percent recovery by this method was excellent (100.14 ± 2.85). Elemental oxide quantities in terms of SiO₂. Al₂O₃, Fe₂O₃, MgO, CaO and K₂O determined by atomic absorption/flame emission (AA/FE) spectroscopy were in good agreement with values measured by x‐ray fluorescence (XRF) on the same subsamples (r = 0.89^* to 0.98^**). but somewhat more variable on subsamples seperated from different pretreatments (r = 0.70^* to 0.97^** ). The method, which has also been tested on 36 additional clay samples from a variety of Kentucky soils with total percent recoveries ranging from 96.5 ‐ 103.5%. demonstrated no bias due to mineralogy with respect to mixed, montmorillonitic. and siliceous classes. This technique presents numerous advantages over other elemental analysis techniques utilizing fusion, dissolution, or XRF spectroscopy with respect to time, effort and cost. With the introduction of inductively‐coupled plasma (ICP) emission spectroscopy. efficiency can be additionally improved.     

Transformation of clay minerals in nanoparticles of several zonal soils in China

Purpose

Clay minerals significantly affect the physical, chemical, and biological processes of soils. They undergo spontaneous modification and transformation depending to the climatic conditions. Information concerning the compositions and transformation of clay minerals in nanoparticle colloids (NPs) (25–100 nm) is severely lacking. Studying clay mineral transformation is important approach to understand soil formation. This study was conducted to determine the transformation sequence of clay minerals in several zonal soil NPs.

Materials and methods

Four soils (Haplustalf, Alf-1; Hapludalf, Alf-2; Hapludults, Ult-1 and Ult-2) were collected from B horizons developed under three different climatic zones of China. Alf-1 (36° 05′ N and 117° 24′ E) was located under a warm temperate zone and Alf-2 (30° 38′ N and 115° 26′ E), Ult-1 (29° 13′ N and 113° 46′ E), and Ult-2 (19° 27′ N and 109° 17′ E) under a subtropical zone. The clay particles (<?2000 nm) (CPs) and nanoparticles (25–100 nm) (NPs) of tested soils were separated. The element composition of CPs and NPs was identified by microwave digestion method. The mineralogy and chemical bonding of clay minerals were studied by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR).

Results and discussion

With decreasing latitude, NPs and CPs showed that the molar ratio of SiO₂ to Al₂O₃ trends to diminish, indicating the phenomenon of desilication and allitization in the tested soils. XRD analysis revealed that the main clay mineral of Alf-1 NPs was illite, followed by vermiculite, kaolinite, and kaolinite interstratified minerals (KIMs). The clay minerals of Alf-2, Ult-1, and Ult-2 NPs were dominated by kaolinite (and KIMs), followed by illite, with a little content of hydroxyl-interlayered vermiculite (HIV) in Ult-1 NPs and trace content of gibbsite in Ult-2 NPs. With decreasing latitude, vermiculite and HIV decreased in NPs. When compared to CPs, smectite as well as illite-vermiculite mix-layer mineral (I-V) and illite-HIV mix-layer mineral (I-HIV) were not detected in NPs. The analysis of d060 region by XRD showed that with decreasing latitude, the main clay minerals in NPs were dioctahedral minerals (e.g., illite or kaolinite). These clay minerals resulted from the transformation of trioctahedral minerals in CPs. The disappearance of 2:1 swelling minerals and trioctahedral minerals showed that the NPs were more susceptible to weathering than CPs.

Conclusions

With decreasing latitude, the transformation of clay minerals followed the sequence of illite?→?HIV?→?kaolinite?→?gibbsite in tested NPs.

     

Properties,weathering and classification of some soils formed in peralkaline volcanic ash in Kenya

Physical, chemical and mineralogical properties were determined for six profiles in and west of the Great Rift Valley in Kenya. Data include morphology, information on gross composition of horizons (organic carbon, cation exchange capacities, extractable cations, etc.), and detailed characterization of the clay fractions by means of transmission electron microscopy, X-ray diffraction, infrared spectroscopy and additional techniques.The three least weathered profiles (Nos. 1–3 of Table I) have morphologies typical of Andepts but lack certain other characteristics common to such soils. Their clay fractions were largely amorphous to X-rays and consisted mainly of poorly ordered siliceous Feoxides with virtually no allophane. All of the clays contained halloysite. The peralkaline nature of the ash parent-material seems responsible for the clay mineralogy of the soils which differs from that generally found in Andepts. The high proportions of iron in the amorphous materials depart from the composition widely reported for such soils. One distinctive feature was the presence of pantelleritic trachyte, found in ash from a number of sites in addition to those of the profiles.How the six profiles may best be classified is an open question. None of the profiles qualifies as Andept. Nor would they be included in the proposed order of Andisols as presently defined. Modifications of the definition of Andisols so as to include some of these soils would seem desirable.     

Dissolution of organohetallic complexes and silica from the clay fraction of podzolic soils

Abstract

The Ae, Bhf and Bf horizons of two podzolic soils from the Appalachian and Laurentian Highlands were treated with various reagents to remove the amorphous material prior to X‐ray diffraction analysis. Treatments were Na citrate, NaOH, Tiron, DCB and modified DCB, with a lower solid:liquid ratio. Samples treated with NaOH, Tiron and DCB were subsequently extracted with citrate. The latter extraction was necessary to remove Fe₂O₃ and SiO₂ that was not solubilized in the first treatment. The effectiveness of the reagents to extract SiO₂, Al₂0₃ and Fe₂O₃ decreased in the following order:

DCB 1:1 > Tiron = DCB > citrate > NaOH

The total weight loss of the samples represented about 1.8 times the sum of the oxides and reached up to 70% of the Laurentian Bf sample. Organic matter accounted for a part of the weight loss and its removal was more complete in the less crystalline samples of the Laurentian profile. Tiron was the best reagent to improve the X‐ray diffraction patterns, closely followed by DCB 1:1 treatment.

Removal of amorphous material and organic matter resulted in a decrease of the cation exchange capacity of the clay fraction, from a maximum of 73.5 meq / 100 g in the Laurentian profile to a minimum of 3.2 meq / 100 g in the Appalachian profile.

The results suggested that in the Laurentian profile, very poorly crystallized minerals possibly contributed to a part of the extracted material.     

Clay fraction determinations with a beta‐ray gauge

Abstract

Comparative measurements of the clay fraction of soils were made with a beta‐ray gauge system, a density meter, and a hydrometer. Reliable clay fraction determinations could be made by a beta‐ray gauge, and a density meter in less than 25 minutes of sedimentation. The beta‐ray gauge measured clay fractions were not affected by surface tension which was the possible cause for variable results obtained with the gamma‐ray attenuation technique.     

CLAY DISPERSION IN TYPICAL SOILS OF NORTH CAMEROON AS A FUNCTION OF PH AND ELECTROLYTE CONCENTRATION

Knowledge of clay dispersion behaviour [which is highly influenced by ion concentration in the aqueous phase and by related surface charge (SC) of colloids] is important for rating soil erosion risk (by water). It can also be useful for improving soil management systems. Clay fractions separated from samples of the A‐horizon of a Vertisol, Ultisol and Oxisol were collected, representing typical soils of North Cameroon. These soils were very different in physicochemical and mineral parameters. The effect of pH and the multivalent ions Ca²⁺, SO₄²⁻ and PO₄³⁻ on SC and dispersion characteristics were determined. The water dispersible clay was found to be higher in the Vertisol and Ultisol than in the Oxisol, indicating that the <2 µm fractions from the Vertisol and Ultisol are more dispersible than that from the Oxisol. The clay dispersion ratio together with the dispersion ratio were found to be in good agreement with water dispersible clay and are negatively correlated with the amount of organic matter and dithionite citrate bicarbonate soluble Fe and Al. Generally, SC of the <2 µm fraction was found to be negative when the pH was in the region of 3 to 9; thus the absolute value is highly pH‐dependent. At pH 6 and 8, CaCl₂, Na₂SO₄ and Na₂HPO₄ additions had antagonistic effects on SC: Ca²⁺ increased SC, whereas SO₄²⁻ and PO₄³⁻decreased SC indicating the adsorption of positively as well as negatively charged multivalent ions by soil colloids. Along with the increase of SC, there was a fall in repulsive forces and formation of Ca‐bridges, the addition of Ca²⁺ induced flocculation more rapidly than SO₄²⁻ and PO₄³⁻ amendments. Copyright © 2011 John Wiley & Sons, Ltd.     

Ammonium fixation by soil and pure clay minerals

Abstract

Fixation of the ammonium ion (NH₄ ⁺) by clay minerals is an alternate way of building the nitrogen (N) pool in soil to optimize N crop recovery and minimize losses. Clay minerals (illite, montmorillonite, and vermiculite) and an illitic Portnoeuf soil were used to compare NH₄ ⁺ fixation abilities. Total N determination and X‐ray diffraction analysis were performed on each of the minerals and the Portnoeuf soil controls, and NH₄ ⁺ saturated batches were subsequently desorbed by potassium chloride (KCl) after 4096 hours. Total N was determined for each employing either Kjeldahl digestion only, or pretreating with hydrofluoric‐hydrochloric acid (HF‐HCl) before the Kjeldahl digestion. The total N for the soil was 38% more after pretreatment with HF‐HCl. The total N determined after pretreatment with HF‐HCl for the NH₄ ⁺ saturated and subsequently KCl desorbed minerals was found to be highest in vermiculite. The cation exchange acapacity (CEC) of each of the minerals was determined, and highest CEC was found in montmorillonite [83.07 cmol(+)/kg]. X‐ray diffraction analysis revealed collapse of the vermiculitic clay lattice from an initial d‐spacing of 13.1 angstrom to 10.4 angstrom after desorprion by KCl. This suggested the existence of sequestered NH₄ ⁺ between the 2: 1 vermiculitic clay interlayer lattice.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

How does the Hedley sequential phosphorus fractionation reflect impacts of land use and management on soil phosphorus: A review

The Hedley sequential‐phosphorus (P)‐fractionation method has been used in many countries to study the effects of land‐use and management systems on soil P. Many data sets have been obtained but collectively never have been considered or to goal topic reviewed. Therefore, the objectives of this review were to compile and systematically evaluate these data. The data generated over many years were grouped into temperate, and subtropical and tropical soils of different land use and duration of soil‐management studies. In natural ecosystems, vegetation types and composition and percent of vegetation covers substantially affected all P fractions with pronounced impacts on the labile and moderately labile P. In short‐term studies (≤ 10 y), changes in the labile and moderately labile inorganic P (P_i) fractions were detected when more P (e.g., by factor 5) was applied than commonly recommended for agricultural crops. However, without P application the changes in all P fractions were subtle in temperate soils, but declines were significant in labile and moderately labile P in subtropical and tropical soils. In both temperate and tropical climates, medium (10–25 y) and long‐term (>25 y) cultivation without P application depleted all P fractions, whereas most of P fractions increased with continuous P application, regardless of the amount and source of P. Synthesis of data resulted in multiple‐regression functions which described differences in labile and moderately labile P fractions as function of differences in amount of P application and duration of the experiments. Moreover, the correlation analysis also showed strong association among most of the P fractions. Current limitations in data interpretation of Hedley fractionation can be overcome by the application of ³¹P nuclear–magnetic resonance (NMR) and X‐ray absorption near‐edge fine‐structure (XANES) spectroscopy.     

Acid‐extractable potassium in agricultural soils: Source minerals assessed by differential and quantitative X‐ray diffraction

Different extraction methods are used world‐wide in routine soil analysis to estimate long‐term potassium (K) reserves for plants. In Sweden, K extracted with 2 M HCl at 100°C (K_HCl) is frequently used, although with limited understanding of the phases extracted. In the present study, we quantified the effects of this extraction on soil minerals in particle size fractions ranging from clay to sand, and estimated their relative contribution to K_HCl. The study included three Swedish long‐term agricultural field experiments with texture ranging from loamy sand to silty clay, as well as mineral specimens of K feldspar. Total weight loss of particle size fractions was determined, and quantitative and differential X‐ray powder diffraction (QXRD, DXRD), applied on solids before and after extraction, was used to quantify the dissolution of individual mineral phases. QXRD and DXRD included spray‐drying of samples, addition of an internal standard and full pattern fitting, where a combination of mineral‐standard XRD traces was matched with the experimental one. Our results show that K_HCl was primarily associated with clay minerals concentrated in the two finest fractions (2–20 and < 2 μm). Highly expandable and mixed‐layer phyllosilicates were quantitatively the most important minerals dissolved. The K was released from micaceous layers in mixed‐layer phyllosilicates with a vermiculitic character. Whether di‐ or trioctahedral, a shared property of the dissolved phases was that they were rich in Fe. In the loamy sand, the coarser fractions (20–2000 μm), where feldspars were prominent, accounted for 35% of K_HCl. According to DXRD, there was no significant decrease in K feldspars in any of the samples, and K_HCl data for the feldspar specimens suggest that clay minerals contributed at least 70% of K_HCl also in the loamy sand. Our study provides insights about the soil minerals that contribute to the long‐term K delivery capacity of soils and an explanation for the prior observation that K_HCl is a dynamic fraction that can be affected by management.     

A potential method to incorporate quantity/intensity into routine soil test interpretations

Abstract

Exchangeable potassium (K), extracted with 1M ammonium acetate, widely used as the measure for plant available K does not estimate the K supplying capacity of the soil. This research was undertaken to quantity the K supplying capacities of some Missouri soils and evaluate a modified K Quantity‐Intensity (Q/I) approach for adaptation into routine soil analysis. The K supplying capacities as analyzed by the modified Q/I and plant removal were measured on the 0–20 cm and 20–40 cm depths of Broseley loamy fine sand (loamy, mixed, thermic Arenic Hapludalf), Mexico silt loam, (fine, montmorillonitic, mesic Udollic Ochraqualf), Waldron clay loam [fine, montmorillonitic (calcareous) mesic Arenic Fluvaquemt] and the 0–20 cm of Sharkey clay (very fine, montmorillonitic, nonacid, thermic Vertic Haplaquet). The dominant clays in the clay fractions were identified by X‐ray diffraction to be composed of montmorillonite and illite. The high linear coefficient of correlation (R₂ = 0.92**) between the potassium buffer capacity index (KBC Index) and cation exchange capacity [CEC, sum of exchangeable Ca, Mg, K, Na, and Neutralizable Acidity (NA)] suggests that KBC Index of soils with similar clay mineral compositions, but different clay quantities, could be estimated from the measured CEC. Plant K uptake was highly linearly correlated with K quantity (Kq, R₂ =0.98**) as measured by the modified Kq/i method. It appears to be possible, using the KBC Index derived from the CEC, to calculate a Kq/i value with a single measurement of the K in equilibrium with 0.01 M CaCl₂. With the modified Kq/i method, and using this approach, a total plant available K model is presented. This modified Kq/i approach offers the opportunity for soil testing laboratories to complete a calculation for total plant available K with only one additional measurement of the equilibrium K in 0.01 M CaCl2. This would facilitate the fine tuning of soil test interpretation by basing K fertilizer recommendations on the quantity of plant‐available K in the soil.     

Forms and buffering potential of aluminum in tropical and subtropical acid soils cultivated with Pinus taeda L

Purpose

Several interactions between Al and the solid phase of soil influence Al buffering in soil solution. This work evaluated soils cultivated with Pinus taeda L. to determine Al forms in organic and mineral horizons using various extraction methods and to relate acidity with clay mineralogy.

Materials and methods

Organic and mineral horizons of 10 soil profiles (up to 2.1 m deep) in southern Brazil were sampled. Organic horizons were separated into fresh, aged, and fermented/humified litter. The following Al extraction methods were utilized: 0.5 mol L^?1 pH 2.8 CuCl₂–Al complexed in organic matter; 1.0 mol L^?1 KCl–exchangeable Al; water–Al soluble in soil solution; HF concentrated?+?HNO₃ concentrated?+?H₂O₂ 30% (v/v)–total Al. Six sequential extractions were carried out to isolate different forms of amorphous minerals that can buffer Al on soil solution: 0.05 and 0.1 mol L^?1 sodium pyrophosphate; 0.1 and 0.2 mol L^?1 ammonium oxalate; 0.25 and 0.5 mol L^?1 NaOH. Samples of clay were also analyzed by XRD.

Results and discussion

There was a clear effect of litter age on increasing total Al concentration. In the aged litter and fermented and/or humified litter, levels of total Al were 1.4 to 3.8 and 1.5 to 7.8 times greater than in fresh litter, respectively. The CuCl₂ method had higher Al extraction capacity than the KCl method for litter. The lowest Al–pyrophosphate values were observed in the Oxisol, which also had a predominance of gibbsite and the lowest levels of Al–KCl and Al–CuCl₂. There was an inverse relationship between degree of soil weathering and soluble and exchangeable Al in soils. Available Al increased with higher Si proportion in minerals of the clay fraction (2:1?>?1:1?>?0:1).

Conclusions

The worst scenario was soils with the combination of high soluble and exchangeable Al levels and high concentrations of amorphous forms of Al minerals. The best predictors of Al accumulation in the youngest litter horizon were extractions of amorphous minerals with pyrophosphate and NaOH. These extractors are normally used to predict the level of Al buffering in soils. Organic matter had less influence on Al dynamics in soils.

     

Characteristics of the soils developed under broad-leaved evergreen forests in okinawa prefecture and the kinki district with special reference to their pedogenetic processes

Abstract

Properties of sesquioxides, clay mineralogical composition, and charge characteristics of the soils developed under broad-leaved evergreen forests in Okinawa Prefecture (subtropical climate) and the Kinki District (warm temperate climate) were studied with special reference to their pedogenetic processes in order to reexamine the corresponding parameters of Brown Forest soils and related soils in Japan.

The soils in Okinawa Prefecture were characterized by a higher degree of weathering as compared to the soils in the Kinki District. Major differences involved the values of the Fed/Fet ratio for the soil samples throughout the profile, and those of the ratios of (Fed-Feo)/Fet, CEC/clay, and (Feo + Alo)/ clay and the content of CaO plus Na₂O for the B horizon. The soils in the Kinki District did not show andic soil properties, nor Al translocation in the profile and, both of which were characteristic of Brown Forest soils developed under cool temperate climatic conditions at high altitudes in the same District.

The difference in the degree of weathering were reflected on the charge characteristics at the very surface of the soils, i.e., the surface of the particles of the soils in Okinawa Prefecture exhibited a lower reactivity as compared with those of the soils in the Kinki District.     

Suitability of a hydraulic‐conductivity model for predicting salt effects on swelling soils

Many empirical approaches have been developed to analyze changes in hydraulic conductivity due to concentration and composition of equilibrium solution. However, in swelling soils these approaches fail to perform satisfactorily, mainly due to the complex nature of clay minerals and soil–water interactions. The present study describes the changes in hydraulic conductivity of clay (Typic Haplustert) and clay‐loam (Vertic Haplustept) soils with change in electrolyte concentration (TEC) and sodium‐adsorption ratio (SAR) of equilibrium solution and assesses the suitability of a model developed by Russo and Bresler (1977) to describe the effects of mixed Na‐Ca‐Mg solutions on hydraulic conductivity. Four solutions encompassing two TEC levels viz., 5 and 50 mmol_c L^–1 and two SAR levels viz., 2.5 and 30 mmol^1/2 L^–1/2 were synthesized to equilibrate the soil samples using pure chloride salts of Ca, Mg, and Na at Ca : Mg = 2:1. Diluting 50 mmol_c L^–1 solution to 5 mmol_c L^–1 reduced saturated hydraulic conductivity of both soils by 66%, and increasing SAR from 2.5 to 30 mmol^1/2 L^–1/2 decreased saturated hydraulic conductivity by 82% and 79% in clay and clay‐loam soils, respectively. Near saturation, the magnitude of the change in unsaturated hydraulic conductivity due to the change in TEC and SAR was of 10³‐ and 10²‐fold, and at volumetric water content of 0.20 cm³ cm^–3, it was of 10¹⁴‐ and 10⁶‐fold in clay and clay‐loam soils, respectively. Differences between experimental and predicted values of saturated hydraulic conductivity ranged between 0.6% and 11% in clay and between 0.06% and 2.1% in clay‐loam soils. Difference between experimental and predicted values of unsaturated hydraulic conductivity widened with drying in both soils. Predicted values were in good agreement with the experimental values of hydraulic conductivity in clay and clay‐loam soils with R² values of 0.98 and 0.94, respectively. The model can be satisfactorily used to describe salt effects on hydraulic conductivity of swelling soils in arid and semiarid areas, where groundwater quality is poor.     

Influence of geogenic CO2 on mineral and organic soil constituents on a mofette site in the NW Czech Republic

Geogenic CO₂ emission on mofette sites may be a factor in soil formation. To demonstrate a CO₂ effect, we studied soils (0–60 cm depth) along a transect across a mofette in the NW Czech Republic. We determined CO₂ partial pressures (p(CO₂)), and the contents in the soil of carbon (C), nitrogen (N), sulphur and dithionite‐ and oxalate‐extractable iron and manganese. X‐ray diffractometry (XRD) and Fourier‐transform infrared (FTIR) spectroscopy methods were applied to the soils' particle‐size fractions. The CO₂ partial pressures varied considerably (0.001–1) along the transect and were positively correlated with both the C_org contents (5.5–432.9 g kg⁻¹) and the C:N ratio (9.3–32.2), indicating a decreased turnover of organic parent material with increasing CO₂. When the soil atmosphere was entirely composed of CO₂, pedogenic Fe oxide contents were small (minimum 0.5 g dithionite‐extractable Fe kg⁻¹) and poorly crystalline. XRD and FTIR spectroscopy revealed primary and secondary minerals such as quartz, feldspars, mica, illite, kaolinite and halloysite irrespective of CO₂ contents. A pronounced effect of CO₂ was found for soil organic matter (SOM), because the FTIR spectra did not reveal a normal accumulation of alkyl C and lipids of microbial origin in the clay fraction. This indicates that microbial synthesis and/or degradation of plant‐derived aliphatic species were reduced. We did not detect more organo–mineral associations, microbially formed polypeptides or pectin in clay fractions in comparison with the clay‐plus‐silt fractions at large p(CO₂). This indicates relatively unaltered particulate OM in the clay fraction. At large p(CO₂) values, the IR bands indicative of lignin became detectable and that of aryl ketones in lignin was positively correlated with p(CO₂). Thus, we suggest that microbial formation of SOM and degradation of lignin is restricted under an increased CO₂ atmosphere. We attribute less humification at increased CO₂ in the soil atmosphere to a decrease in oxidative transformations and decreased microbial activity.